Dyes of the anthraquinone series



a man Patent 650,057.

PatentedNov. 21 1944 e UNITED ESTATES; PATENT- OFFICE- i 32,36 3Q04? DYES on THE ANTHRAQUINONE sERIEs Edwin c. Buxbauin, Media, Pal, assignmto E. I. du Pont de Nemours & Company, Wilmington, Del acorporation of'Delaware 1 No Drawing. Application October 24, 1942,

A Serial No. 463,247 5 Claims. (01. 260-303) This invention ,relates to the preparation of new dyes of the anthraquinone series, and more particularly; to the preparation of new diamino- 1 isothiazoleanthrone compounds particularly useful as dyes for W001, silk, nylon and cellulose ace- 'tate, and for use as intermediates in the preparaeral dyes hayebeen producedwhich contain the isothiazoleanthrone nucleus; there has been little work done in producing wool, silk, or cellulose acetate dyes containing this nucleus,;' probably because the ones investigated appeared to retain the known tendency of the nucleus to give colors which dyein yellow and brown shadesr See Gerthus making ayailable a large number of colors varying in shadej fromthose already available The present invention has for its object the preparation of a new series ofdyes of the anthraquinone classpwhich dye in green and blue shades wool and silk, but which are :also useful in the dyeing of nylon and cellulose acetate and for the and which are useful not only for the dyeing of" coloring of gasoline and other petroleum oil fra c- 1 i tions, and which may serve as'intermediates for i the preparation of new Ivat dyes.

-These new dyes of the isothiazoleanthrone v series. which dyein green andblue shades, can

y be produced by introducing amino or substituted amino groups into the isothiazoleanthrone nucleous in the 5- and 8-positions. The benzene further substituent, halogen or a sulfonic acid radical. The compounds of the present invention, therefore have the following general formula in which each R stands for a substituent ofthe ring of the isothiazoleanthrone molecule which I carries the amino groups may also carry, as a and in some cases permitting the preparation of less expensive colors of equal or improyed, properties to replace. those employed today. The

5-amino-, or rl8famino -LQ-isothiaZOleanthrQnes, y e n y p i 1 or the correspondingalkylaminoisothiazoleanri While in the anthraquinone vat dye classseypreparation of the colors of this series, are pre pared by the known methods, such as by the treating of the 1-amin0-5- anthl'aquinone sulfonic acid or the corresponding l nitro-derivative with sodium sulfide, sulfur and an. alkylamine or ammonia. The aminoisothiazoleanthrone1is then halogenated, or the amino group may fir st be acylated and then the product may be 'haloby genated. The halogen is thus introduced in the 8- or the 6 andB-positions, depending upon whether the amine group is substitutedor not and the nature of the substituted amine group. The halogen in the 8-position is then readily substituted' by ajlarge variety of amines or am monia, and the freeamine may be acyla'ted by known methods. It is thus possible to produce alarge number of new compounds which vary in shade in the green and blue range.

" The following examples are given to illustrate the invention. Parts used are by weight."

Example 1 One hundred and fifty-one parts iof 5-a1nino 1,;9-visothiazo1eanthrone are suspended in 6 6O parts of nitrobenzene. The suspension is heated to 135'-140 C. until all water has been rernoyed. It is then cooled to 85 C. and there are then added 3 parts of iodine. The mass is heated to 85 C. and there is then added, over a periodof four hours, a mixture of 102 parts of bromine and 102 parts of sulfuryl chloride. When the bromination has been completed the mass is cooled to room temperature, filtered, washed with nitrobenzene and alcohol, and finally with hot water.

" It is dried at 1097-110 C. The orange colored 6,8-dibrorno{1,9-isothiazo1eanthrone.

compoundwhich is formed consists of 5-amino- It has a melting point of 273 C. i e

Twenty-one parts of this; product are mixe with 80 parts 'ofaniline, 20 parts of arhmoniu acetate, parts of watenand 0.3 part of basi copper acetate, and the mixtu're'is heatedfwith agitation at reflux i temperature for a period of eight hours. It is then cooled and diluted with 160'part of ethyl alcohol. The precipitated compound is filtered ofi, washed and'dried. It consists of -amino-6-bromo-8-anilino 1,9 isothiazoleanthrone, which dissolves in strong sulfuric acid with a red-brown color and gives a reddishblue solution in organic solvents.

Example 2 Fifty-one parts .of 5-amino-1,9-isothiazoleanthrone are dissolved in 200 parts of 93% sulfuric acid. When solution is complete,the acid mass is poured into 1300 parts of cold water. then added, over a period of ten hours at ,2,535 0., 342 parts of a sodium bromide-sodium bromate solution containing 6.96% of sodium bromate and 9.35% of sodium bromide, which efiects the i. .1- troduction of two atoms-of bromine.

When the bromination is finished, the suspended compound is filtered off, washed acid-free and dried, ,"It is 3 are dissolved in 200 parts of 93% sulfuric acid.

identical with the product prepared in Example 1 and consists of 5-amino-6,8-dibromo-l,9-iso thiazoleanthrone.

Twenty-one parts of this product are added to There is 160 parts of p-toluidine, 10 parts potassium a'cetate' and 0.2 part of basic copper acetate. The mixture is heated to 14014,5 C. for five hours. It is then cooled to 80 C.; and there are then added 320 parts of ethyl alcohol. The diluted reaction" mass is filtered and'the filter cake is washed and dried. The resulting 5-amino-6- bromo-8-p-toluidino-1,9-isothiazoleanthrone dissolves in benzene, gasoline and other organic sol-.

vents with a bright blue color of good tinctorial strength. It dissolves in strong sulfuric acid with a yellow-brown color which changes to a bright yellow-green upon the addition of trioxy-methylene. 226.5 C.

Example 3 5-amino-1,9-isothiazoleanthrone is benzoylated in ortho-dichloro-benzene with benzoyl chloride to form 5-benzoyl-amino-1,9-isothiazoleanthrone. This compound is then suspended in a mixture of glacial acetic acid and nitrobenzene and heated to l00-10,5 C. Sufiicient chlorine is then added until one atom of chlorine has been introduced.

Eight parts of the resulting 5-benzoy1amino-8- chloro-1,9-isothiazoleanthrone are heated with 100 parts of aniline, 5 parts of potassium acetate and 0.25 part of basic copper at a temperature of 170-180 C. for a period of two to three hours."

The reaction mass is then cooled, diluted with ethyl alcohol, filtered, washed and dried, The resulting 5 benzoyl amino 8-anilino-1,9-"isothiazoleanthrone is a dark blue powder which dissolves in benzene, gasoline and other organic s01- vents with a pure blue color. It dissolves in concentrated sulfuric acid with a maroon color which changes to a. grayish black upon the addit on of trioxymethylene. It has a melting point of 248 C.

Example 4 Twenty parts of the 5-benzoylaniino-8-anilinol,9isothiazoleanthrone prepared as in Example The compound has a melting point of Example 5 Fifty-nine parts of 5-benzolyamino-1,9-isothiazoleanthrone are suspended in 264 parts of nitrobenzene. The mass is heated to 135140 C. and held until completely dehydrated. It is then cooled to 85 C. and 1 part of iodine is added. There is then added a previously prepared mixture of 16 parts of bromine and 16 parts of sulfuryl chloride over a period of four hours at 85 C. The bromination mass is then cooled to 30 C., filtered, washed with nitrobenzene, then with alcohol, then with hot water, and dried. This re sulting 5-benzoylamino-8-bromo-1,9-isothiazoleanthrone is hydrolized in 93% sulfuric acid at C. to give the 5-amino-8-bromo-1,9-is0thiazoleanthrone, which is a bright orange powder with a melting point of 255 C.

Twenty-five parts of the 5-amino-8-bromo-l,9- isothiazoleanthrone are heated with 200 parts of p-toluidine, 13 parts of potassium acetate and 0.5 part of basic copper acetate at l70-180 O. for six hours. After cooling, the condensation mass isdiluted with ethyl alcohol and filtered. The resulting 5-amino-8-p-toluidino-1,9-isothiazoleanthrone is a blue product which dissolves in organic solvents, such as benzene and gasoline, with a pure blue color of excellent tinctorial strength. 1

In place of p-toluidine, alpha or betanaphthylamine may be employed to give the corresponding 5-arnino-8-naphthylamino-l,9-isothlazoleanthrone.

Example 6 Five parts of 5-amino-8-p-toluidino-1,9-isothiazoleanthrone are dissolved at 30 C. in 100 parts of sulfuric acid monohydrate. When sulfonation is complete, the acid mass is poured into.

450 parts of ice and water and the product filtered off, washed acid-free with brine'and dried. V i i This sulfonic acid derivative dyes wool in bright blue shades, and has good leveling prop- .erties, Other arylamino compounds can be used in place of the p-toluidine to give a variety of other shades, all ofwhich exhibit the same brightness and good application properties. For instance, sulfonated 5-amino-8-anilino-1,9 isothiazoleanthrone dyes in red-blue shades; sul-' fonated 5-amino- 8-p-xylidino-1,9-isothiazoleanthrone dyes in navy blue shades, and sulfonated 5-amino-8 orthotoluidino 1,9 isothiazoleanthrone dyes a reddish-blue on wool, which is not as red as the ani1ino-derivative.

, Example 7 7 Sixty-three and one-half parts of 5-methylamino-1,9-isothiazoleanthrone, prepared as described in Ann. 393, 191 by Gattermann, are dissolved in 500 parts of nitrobenzene containing 30 parts of sodium carbonate. The mass is heated to C. and, while holding at this temperature,

there are added 28 parts of bromine. After cooling, the newly formed 5-methylamino-8-bromo- 1,9-isothiazoleanthrone is filtered off, washed and dried.

' Ten parts of the 5-methylamino-8 bromo-1,9 isothiazoleanthrone is reacted with parts of para-toluidine in the presence of five parts of potassium acetate and 0.2 part of basic copper acetate at 1 70-.180 C. for six hours. The mass is cooled and diluted with ethyl alcohol.

The newly formed 5-methylamino-iietoluidinoe ,l,9-i sothiazoleanthrone precipitates in excellent crystalline form. This compound dissolves in organic solvents with a greenish-blue color, and has very good tinctorial strength in gasoline.

gives a dye of good application properties which colors wool in bright greenish-blue shades. By substituting other amines such as aniline,

When sulfonated by any of the usual methods it xylidines, anisidine, amino-diphenyl ether, or

can be obtained. l

Example 8 One hundredand twenty-six parts of -amino- 1,9-isothiazoleanthrone are suspended 111.;650

, parts of ortho-dichlorobenzene and heated to 150-160 C. until completely dehydrated. The

mass is cooled, to 20-25 C., and 64 parts of chlorosulfonic acid are then added at 20-25 C.

over a period of from one to two hours. The temperature is raised to 152 C. over a period of two hours and held at this temperature for ten hours. i The mass is then cooled to 60-'70 C.,

made alkaline with soda ash, and then steam] distilled free of solvent. The water soluble sodium sulfonate of 5-amino-1,9-isothiazoleanthrone is acidified with 124 parts of 18% sulfuric acid. There is then added, overa period of ten hours at 20-25 C., a solution of 58 parts of mining salts in 250 parts of water. The mass is heated to the boil, boiled 30 minutes, and filtered hot. The filtrate is neutralized with sodium carbonate, and the brominated sodium sulfonate of fi-amino 1,9 isothiazoleanthrone is precipitated out of the solution, filtered off, washed withcold water and dried; Five parts of the 5 amino 8 bromo 1,9 isothiazoleanthrone-sodium sulfonate is boiled for two hours with parts of cyclohexylamine, 3 parts of sodium carbonate, 0.25 part of copper sulfate, parts of ethyl alcohol and 225 parts of water.

- The bronze-colored 5 amino 8 cyclohexylamino-l,9-isothiazoleanthrone sodium sulfonate which separates out is filtered off after cooling, washed, and dried. It has good application properties and dyes wool in clear reddish-blue shades.

Example 9 Forty-three and one-half parts of 5-benzoylamino 8 bromo 1,9 isothiazoleanthrone are heated with 22 parts of paratoluene sulfonamide, 13 parts of sodium carbonate, 1.0 part of cuprous chloride and 225 parts of ortho-dichloro-bena zene at reflux temperature for three hours. When the reaction is completed, the mass is cooled to 80 C. and diluted with 300 parts of The crystalline 5-benzoylamino- 8 p toluene sulfonamido 1,9-isothiazolean throne is filtered off, washed with ethyl alcohol.

water, and dried.

alcohol and hot.

amino-diphenyl, wool dyes of modified shades Forty-two parts of this compound are dissolved in 340 parts of 96% sulfuric acidat 30 C. and

held at this temperature until hydrolysis of this The resulting, 5- benzoylamino-S-amino-LQ isothiazoleanthrone compound has taken place.

is a violet colored compound with a melting point of 313 C. It is a useful intermediate for further condensation, particularly in thevast acid derivatives of said compounds, the halogen in which each R stands for a substituent of the shades differing somewhat from the color on cellulose acetate, and exhibits good application properties. i

I claim: 1. The 1,9-isothiazoleanthrone compounds 0! the formula:

' R-NH 1 I s in, which each a stands for a substituent of the group consisting of H, alkyl, aralkyl, cycloalkyl, acidyl, sulfonyl and aryl of the benzene and naphthalene series, and the halogen and sulfonic when present in the molecule being one of th positions 6 and '7.

2. The 1,9-isothiazoleanthrone compounds of the formula:

group consisting of H, alkyl, aralkyl, cyclo'alkyl.

acidyl, sulfonyl and aryl of naphthalene series.

3. ,8-anilino-5-amino-1,9-isothiazoleanthrone. 4. 8-toluidino-5-methylamino-1,9 isothiazoleanthrone.

5. 5,8-diamino-1,9-isothiazoleanthrone.

' EDWIN C. BUXBAUM.

the benzene and 

